Oxime azo dyestuffs



Patented Dec. 6, 1955 United States Pate iit OfiFice 726,238

1 r 2 h 2,726,238 textile materials or as pigment according to their solu- OXIME AZO DYESTUFFS bility.

Heinrich Morschel, Leverkusen, and. Karlfried Wede- T dyohlgs containing metal Produced and obtained In meyer, Leverkusen-Bayerwerk, Germany, assignors to One of the described Ways are distinguished by cleamess Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, 5 of the shades, good fastness to light and,vfirst of all, by a Germany, a corporation of Germany good fastness to washing.

No Drawing. Application February 16, 1954, The new dyestuffs oifer also the advantage that due to Serial No. 410,730 the presence of the ortho-hydroxy-aldoxime or -ketoxime Claims priority, application Germany February 26, 1953 grouping they need less acid salt forming solubilizing 7 Cl i (C1, 260 160) 10 groups than comparable dyestuffs in order to be sufli- The present invention relates to metal complex formcienfly soluble i the dyefbath; this yaiemlubilizing ing azo dyesmfis, the metal complex compounds thereof ortho-hydroxy-oxime-groupmg characteristic for the new dyestufis however is blocked in metal complex formaand to a process of making the same; more particularly it relates to azo dyestuffs mono and polyazo tron and therefore loses 1ts solubillzing properties where- Stufis containing at least once a hydroxy group and in by dyeings of increased fastness to washing must be obtained. 232 12 32:3 22332; iggzfig hf gigg group The following examples illustrate the invention with- The new dyestuffs are obtained by selecting in the usual however lumtmg It thereto synthesis of azo dyestuffs the components in such a way Example 1 that the dyestuffs formed contain at least once in the molecule a hydroxy group and in ortho-position thereto a ketoXime or an aldoxime group. The new dyestuffs may further contain the usual substituents. Thus it may be expedient that starting components are used which contain further complex forming groups e. g. the ortho-hydroxy-carboxylic acid grouping, or hydroxy-, alkoxy-, carboxy-, oxyacetic acid and amino groups in o,o'-position to an azo bridge. The new dyestufis may be mono- Tetrazotized 4,4'-diaminodiphenyl obtained in customary manner from 18.4 grams of 4,4'-diaminodiphenyl by diazotization in hydrochloric acid medium is run in at 5 C., into a solution of' 31.5 grams of o-hydroxyacetophenone oxime in 800 cc. of Water and 17 grams of NaOH, the mixture being kept alkaline by adding sodium carbonate. After the coupling is completed. the mixture is adjusted to pH 8-9 by means of hydrochloric acid or polyazo dyestuffs prepared from diazo, diazoazo or under heating to 80 C. The separated dyestuif is filtered tetrazo compounds; the characteristic ortho-hydroxyand dried. It corresponds to the formula:

0 HON: I =NOH lHa V CH3 When dyed on cotton and after-coppered, the dyestufl? yields a reddish yellow of excellent fastness to washing.

' Example 2 Q 55.5 grams of 4,4-diamino-3,3-dihydroxydiphenyl-dihydrochloride are diazotized in 1000 cc. of water and ketoxime or -aldoxime grouping can be present once or several times in the dyestuflf molecule, it can be present, in the radical of the diazo component or in the radical of 4 the coupling component or in both.

In the manufacture of the new dyestufis not onlysuch components can be used as contain already the orthohydroxy-ketoxime or -aldoxime grouping, but also comof hydrochloric a With grams of NaN02 pounds which contain an ortho-hydroxyketo or -aldeat C- 'After neutralizing with 16 grams of Sodium hyde grouping; in this case the carbonyl groups are transcarbonate the diazonium compound is sucked ofi, washed fgrmed i l manner i h k t i or ld i with water and thereafter pasted with 1000 cc. of Water. after coupling. It may also be expedient to choose for The Paste of the diazotized ythe formation of the dyestuffs such components as contain droxydipheflyl is added to a Solution of 67-25 grams of in ortho-position to a ketoxime or aldoxime group or resacetophenoneoxime in 1500 cc. of water and 28 grams to a keto or aldehyde group a group that can be changed f a H at 5 C. After 8 hours the temp is into a hydroxy group e. g. a methoxy group, or c n be allowed to rise to room-temperature, and the mixture is exchanged for a, hydroxy group e, g, halogen, and after stirred for further hours. The mixture is then adcoupling is complete to change those groups into or exlooted to P y means of hydrochloric acid, d the change them for hydroxy group In some cases it may dyestutf is salted out with sodium chloride. After filteralso be advantageous, if the diazo component bears the ing and drying a dyestuff is obtained corresponding to the grouping characteristic for the new dyestuif, to chrome following formula:

HO (i)H HO I I HON:-

' 41H: CH3 the diazo component before the diazotization as this is The dyestufr dissolves in water with a violet color. The done in the manufacture of azo dyestuffs which contain after-coppered dyeing" on cotton is reddish navy-blue and in the diazo component the salicylic acid grouping. shows excellent fastness to washing and very good fast- The new dyestuffs can be converted into their metal ness to light and to brightening.

complex compounds in the usual manner either in sub- If as azo component instead of the 'resacetophenone stance, on the fibre or in the dye-bath. According to oxime the equivalent quantity of resorcylaldoxime, or their constitution the new dyestuffs are suited for the dyeresopropiophenone oxime or resobutyrophenone oxime is ing of fibres of natural or regenerated cellulose, of fibres employed, corresponding dyestufis are obtained that show of animal origin or of synthetic fibres; The metal comsimilar properties with regard to water-solubility, shade plex compounds formed in substance are suited for dyeing on cotton and fastness properties of the dyeings.

3 4 Example 3 Example 5 The diazo solution obtained from 33 grams of 4,4'-di- 28.5 grams of 2-hydroxy.-5-(4'-arninobenzoyl)-aminoaminodiphenyl urea-3,3'-dicarboxylic acid in customer) acetophenone oxime are dissolved in 200 cc. of water and manner by diazotization in hydrochloric acid medium is 4 grams of NaOH, 69 cc. of a percent sodium nitrite run into a solution of 34 grams of resacetophenone oxime 5 solution are added and the mixture is stirred into 225cc. in 800 cc. of water and 21 grains of NaOH at 5 C., the of 2 n hydrochloric acid at 0-2 C. Stirring is continued reaction mixture being kept alkaline by adding sodium for further 30 minutes and the diazotization mixture is carbonate. After the coupling is completed, the separaadded to a solution of 17.5 grams of resacetophenone tion of the dyestuff is accomplished by adding sodium oxime in 500 cc. of water and 53 grams of sodium carchloride. It corresponds to the following formula: 10 bonate. After the coupling is completed, the mixture is (H1 HO O? (l3 0 OH H0 110-- N=N-NH-c 0-HN-N=NQ0H HON: |=NOH H: CH3 Whein dyed on cotton and after-coppered a red-brown adjusted to pH 9 by means of acetic acid, heated to 60- 70 C. and the dyestuff is sucked off. It corresponds to the following formula:

dyeing is obtained showing very good fastness to washing and to light.

Example 4 25.7 grams of 4-amino-3T-carboxy-4'-hydroxy-azobenzene are dissolved in 200 cc. of water and 4 grams of C C O-NH@-OH NaOH, 69 cc. of a 10 percent nitrite solution are added and the mixture is stirred into 200 gramsof ice-water and J; =NOH 35 cc. of hydrochloric acid. To the diazotization mixture thus obtained a hydrochloric acid solution of 12.5 grams of l-amino-Z-methoxy-S-methylbenzene is added at 3 C. and the mineral acid is neutralized by means of The after'coppered dyemg on cotton browmsh sodium acetate. After the coupling is completed the low and Shows very good fasmess to Washmgaminodiazo dyestufl is sucked ofi; the filter cake is pasted mm with 1000 cc. of water and diazotized with 6.9 grams of E P18 6 sodium nitrite in hydrochloric acid medium. The diazo- 354 grams of 5-amino-Z-methoxy-acetophenone oxime tization mixture is stirred into a solution of 18.4 grams ar diaZotiZ d in customary manner in hydrochloric acid of resacetophenone oxime in 1000. cc. of water and 138 di m and coupled with 60 grams of 2-hydroxynaphgrams f di m a bo ate at 3 Q Aft 15 hours th thalene-S-sulfonic acid in sodium carbonate alkaline metemperature is raised to 70 C. and the dyestuff is sucked dillm- The dyesmfi is Salted out at nd fillcred off. It corresponds to the following formula: 05. To the solution of the dyestuff in 2000 cc. of hot ()CHa HO HO N= 0H N800 H| =NOH Ha When dyed on cotton and after-coppered, a bordeaux water, a solution prepared from 80 grams of copper sul is obtained showing very good fastness to washing. t 300 grams of Water, 150 grams of glycerol and 35 The following table contains further combinations. grams of a percent caustic soda solution is added, and Dyestufis obtained from the components: 60 the mixture is kept for 6 hours at 95-100 C., whereby the dyestuff' is coppered with elimination of the methyl s d f it group. The copper complex dyestufi separates. On the DMD component Am component g g g ij next morning it is filtered cold, washed with water and ing on cotton dried. The dyestutf dissolves in water with a blue-red color and represents the copper complex of the monoazo 4,4-d1amin0di pheny1- 2molresacetophenono oxime. violet. dyestutf Of the following formula:

3,3-dioxyacetic acid. 4,4-dtamin0diphenyld0 red-violet.

3,3'-dlcarb0x'yllc acid.

D0 1 mol resacetophenone oxcurrent. HON: H0

iho sh tir fiiii V l am y 0X 8 1ene-7-su1t'onic aZiiL a 'N=N Do 1 mol resacetophenone oxreddish brown.

true, 1 mol 1-pheny1-3- methyl-5-pyrazolone. 8 DIN 4,4 diagngifiodlphenyl- 2mol2,6-d1hydroxynaphthareddish grey.

15323:, carboxylic lene-l-aldoxime. Example 7 Do 2 respropiophenone brgwnlsh bor- 26.4 grams of 1-amino-2,5-dichlorobenzene-4-sulfonic Do 2 2 fififb aciii1 are diazotized in customary manner in hydrochloric ace o enone oxime. aci medium and coupled with 13 grams of o-hydrox 2molmixed ot2- in y f %g fl benzaldehyde in sodium carbonate alkaline medium, 4 5 one ac and 2-h dmxy 5 am1macet0ph% grams of NaOH being used for dissolving the azo corn- I none 12m ponent. After the coupl ng is completed the dyestuff is diaminodlphenyl-m 1 1 8 gafl g i ggi reddish brownfully separated by adding sodium chloride and then sucked gr m s-amnjo-z hy; off. The dyestuff paste is boiled in 1000 cc. of water ffi iifggfi gggfi ggf under addition of 14 grams of hydroxylamine hydrochloresacetophenone oxime. ride and 28 grams of crystallized sodium acetate for 2 hours. On cooling the dyestufi precipitates almost com:

r, 2,726,238 I "I 6 f 7. pletely outof the solution. It corresponds to the formula: the solution of the one sided coupling produ t f:(4'; aminobenzoylamino) -2-aminobei1zoic acid and Z-hydroxyacetophenone oxime obtained according to Example 8 at 0-3 C., stirring being continued until the coupling is com- 5 pleted. The dyestulf is sucked ofi and dried. It corresponds to the formula:

COOH no =NO0 ONHN=NC-C(3Ha HO-ii 1H1 HON= I in" N When dyed on wool and after-chromed, clear orange- When dyed on cotton and after-coppered a reddish brown shades are obtained. yellow is obtained showing very good fastness to washing E xam ple 8 and to light. a g

17.7 grams of 5(4-aminobenzoylamino)-2-amino- 7 Example 10 benzoic acid are suspended in 375 cc. of 2 n hydrochloric 7 grams of 4,4'-diaminodiphenyl-3,3'-dicarboxylic acid acid and 250 cc. of water, to which suspension 90 cc. of a are diazotized in customary manner. A solution of 8.6 10 percent sodium nitrite solution are added at 0 C. grams of 2,8-dihydroxynaphthalene-3-carboxylic acid-6- After stirring for some time, the solution is neutralized sulfonic acid in 200 cc. of water and 25 cc. of 2 11 sodium with sodium carbonate. A suspension of 9.6 grams of 2- carbonate solution is dropped into this diazonium salt soluhydroxyacetophenone oxime in 165 cc. of 2 n sodium tion at 03 C. Sodium bicarbonate is added until a pH- carbonate solution and 125 cc. of water is poured in this value of 7.5-8 is reached. When the coupling is comneutral diazonium salt solution and the mixture is then pleted the suspension of the one sided coupling product stirred for 3 hours at 0-3" C. Thereafter a solution of thus obtained is added to a solution of 11.9 grams of the 25.5 grams of 2-(4-aminobenzoylamino)-5-hydroxynaphmixed urea from 5-amino-Z-hydroxyacetophenone oxirne thalene-7-sulfonic acid in 125 cc. of 2 n sodium carbonate and 2-amino-5-hydroxynaphthalene-7-sulfonic acid in 400 solution is added drop by drop within 10 minutes. After cc. of water and grams of anhydrous sodium carbonate 2 hours 87 cc. of 1 n caustic soda solution are added and at 0 C. After the coupling is completed'the dyestufi is the solution is stirred until the coupling is completed. The salted'out at 80-90 C., sucked ofi while still hot, and dyestulf thus formed is sucked oif, dissolved in '325 cc. of dried. The dyestuff corresponds to the formula:

H000 ooorr OH I I OH HOOC SOsH HOsS NH-C O-NHQ-OH H N0H 1 n caustic soda solution and 1750 cc. of water, 44 cc. of When'dyed on cotton and after-coppered areddish darka 10 percent sodium nitrite solution are added and .690 cc. blue is obtained showing good fastness to washing and of 2 n hydrochloric acid are dropped in with stirring at to light.

03 C. After4 hours this diazo solution is stirred into a solution of 10 grams of 2-hydroxyacetophenone oxime in 500 cc. of 1 n caustic soda solution and the pH-value is r The dyestufi obtained in customary manner by diazomaintained at 8-9 by adding sodium carbonate. When tizing 12.8 grams of the potassium salt of 4,4'-diaminodithe coupling is completed the dyestuif is salted out at phenyl-3,3'-dioxyacetic acid and coupling with 12.6 grams 50'70 C., sucked ofi anddried. It corresponds'to. the of 2-amino-5-hydroxynaphthalene-7-sulfonic acid is disfollowing formula: H I solved in 750 cc. of water and 100 cc. of 1 n caustic soda Example 11' COOH When dyed on cotton and after-coppered a red-brown solution. This solution is mixed with 36 cc. of a 10 percent dyeing is obtained showing very good fastness to washing nitrite solution and then stirred into 300 cc. of 2 n hydroand to light. .7 V chloric acid at 0-3 C. The suspension of the diazonium E mpl 9 s salt thus obtained is stirred into a solution of 8.7 grams 7 7 not 4-methyl-Z-hydroxyacetophenone oxime in 300 cc. of

Aso lution of 11.2 grams of 1-phenyl-3-methyl-5-pyrazo water, 100 cc. of 1 n caustic soda solution and 55 grams lone in 68 cc. of 1 n caustic soda solution is dropped into of anhydrous sodium carbonate at 0-3 C. When the coupling is completed the dyestuff is salted out at 60-65 C., sucked off and dried. It corresponds to the formula:

HO HO OCCHzO bar from to 7, both inclusive, and R' stands for the radical of coupling components selected from the group con- 0 CHSC OOH OH noQrrqw- SOaH Hots N=N-QOH H O N :N O H (1 Ha (kHz When dyed on cotton and after-coppered a grey-blue is obtained showing very good fastness to light and to sisting of radicals of the benzene and naphthalene series containing in a benzene nucleus (1) an hydroxy group and washing. (2) the group We claim: --C=NOH l. Polyazo dyestufis corresponding to the general forg n mula wherein X stands for a link selected from the class Cunsisting of a carbon-carbon-linkage, the radical NHCO, the radical NHCONH-, and the radical -N=N, Y and Z stand for radicals selected from the group consisting of H, -OCH3, OH, COOH and -OCH2COOH, R stands for the radical of a coupling component selected from the benzene and the naphthalene series and containing in a benzene nucleus (1) an bydroxy group and (2) the group in ortho-position to each other, wherein n is a whole numher from 0 to 7, both inclusive, radicals of the benzene series, containing an orthohydroxy-carboxygrouping, and radicals of the benzene, naphthalene and pyrazolone series being coupled in ortho-position to an hydroxy group.

2. Polyazo dyestuffs according to claim 1 where, in the radical of the coupling component, the benzene nucleus containing (1) an hydroxy group and (2) the group in ortho-position to each other, wherein n is a whole number from 0 to 7, both inclusive, is linked to the -N=N- bridge by means of a radical selected from 33 the group consisting of radicals of the benzene and naphthalene series. in ortho-position to each other, wherein n is a whole num- 3. Polyazo dyestutf corresponding to the formula (30011 no =NC GO-NHON=NC--tfi-CH:

H0); N HON= 4. Polyazo dyestufi corresponding to the formula Hooocmo 0.011,.00011 11 H0 311; N=N N=N 0m HO-QN=N sonar H0=S N=NQOH HON: =NOH Ha (13H;

5. Polyazo dyestufis corresponding to the formula:

OH H0 at o 00H 03 6. Polyazo dyestufi corresponding to the formula:

7. Polyazo dyestufi corresponding to the formula:

=NOH 5H3 OOOH H HON= I H033 NH- No references cited. 

3. POLYAZO DYESTUFF CORRESPONDING TO THE FORMULA 